Liquid triaryl phosphates



atented es.

UNITED STES PATENT OFFICE C L I The Dow Company to. assisnor to Application 1, 19

No. ceases 7 Claims. (01. sec-m) invention concerns certain new aromatic phosphates useful as plasticlzing agents my the preparation of cellulose ether plastic compositions.

it o-xenyl phosphate, etc., have been round to be particularly useful for such purpose sincethey of the p-tertiarybutylphenyl phosphates arecrystalline solids at ordinary temperatures; and

this 1 property detracts somewhat from their 25 utility as plasticizing a ents' since they have a tendency to crystallize and to exude to the surface oi the compositions into which they have been incorporated, thereby causing blushing or blooming oi the plasticized compositions.

I have now found that by introducing a methyl group into the ortho pomtion oi the p-tertiarybutylphenyl radical of such triaryl phosphates, it is possible to obtain liquid products which substantially the same desirable plasticiz- 36 1 8 action on cellulose others as do the p-tertiarybutylphenyl phosphates, but which. because oi their liquid state, do not cause blushing oi the compositions into which they are incorporated. The invention, then, concerns the new liquid 40 triaryl phosphates having the general formula:

wherein R represents anaryl radical, and a and n each represents an integer, the sum 0! n and a .being equal to 3i The new p-tertiarybutyl-o-tciyl phosphates having the above formula are prepared by reacting a phosphorus oxyhalide, e. a. phosphorus oxychloride or phoephoms oxrbromide, with ptertiarybutyl-o-cresol and, ii required, with another phenol, e. phenol. creeol, naphthol, pcyclohexylphenol, 2.4-dimethylphenol, etc., or an alkali metal salt thereof. When tri-p-tertiai'ybutyl-o-tolyl phosphate is the product desired, a phosphorus oxyhalide is reacted directly with approximately three molecular equivalents or p-' u tertiarybutyl-o-cresol. When a mixed triaryl phosphate 01 the present class, e. a. p-tertiarybutyi-o-tolyldi-o-xenyl phosphate, di-p-tertiarybutyl-o-tolyl mono-p-ethylphenyi phosphate. etc.. is the product desired, apho'sphorus oxyhalide is reacted with p-tertiarybim l-o-creaol to iorm a p tertiarybutyl-o-tolyl phosphoric acid dihalide or a di-p-tertiarybutyl-o-tolyl phosphoric acid mono-halide, and such intermediate product is then reacted with another phenol to form the desired mixed. triaryl phosphate. It desired, the'order in which the diiierent phenols are reacted may be changed. Thus. a phosphorus oxyhalide may first be reacted with a phenol other than p-tertiarybutyl-o-cresoi to iorm an aryl so phosphoric acid monoor di-halid'e, which prodnot may then be reacted with p-tertiarybutyl-ocresoi to form the desired product.

Each of the above reactions is carried out by heating a mixture of the. necessary reactants to 35 a temperature at which hydrogen halide is evolved from the reaction mixture, preierably in the presence of a catalyst such as metallic calcium, masnesium, or aluminum, or a chloride oi magnesium,aluminum or iron. The reactions are preferably carried out at the lowest convenient temperature, e. 3. below about 200 6., since at higher temperatures by-product formation may occur to an objectionable extent. a

In preparing a mixed triaryl phosphate of the present class from a phosphorus oxyhalide and the necessary phenolic compounds, the intermediate phosphoric acid halide product may be separated and purified, e. g. by fractional distillation, before carrying out the successive reaction for the formation of the mixed triaryl phosphate product. In practice, however, it is usually more convenient merely to distill any unreacted phosphorus oxyhalide from the crude intermediate aryl. phosphoric acid halide, add the necessary proportion of the second phenol, and continue the reaction as hereinbefore described to obtain the final product. After the reactions for the formation of the triaryl phosphate product are completed, the reaction mixture is usually blown with air or washed with water to remove hydrogen halide therefrom The resulting product consists largely of a single mixed triaryl phosphate, but may contain a minor proportion of a second mixed triaryl phosphate as well as some symmetrical triaryl phosphate formed by over-reaction of one of the phenolic reactants with the phosphorus oxyhalide in the initial stage of the process. Such impure mixed phosphate product is adapted to most of the uses to which the pure compound is suitable and, accordingly, is a valuable product. When desired, the individual phosphates contained in such product can usually be separated by fractional distillation.

The following examples will illustrate several ways in which the principle of the invention has been applied but are not to be construed as limit ing the same:

Example 1 A mixture of 246 grams (1.5 mole) of p-tertiary-butyl-o-cresol, 77 grams (0.5 mol) of phosphorus oxychloride, and 2 grams of magnesium metal was heated at a temperature of 160 C. for six hours. after which time the mixture was blown with air for two hours. A total of 1.45 mols (96.7 per cent of the theoretical) of hydrogen chloride was evolved from the mixture during the reac-- tion. The mixture was dissolved in an equal weight of o-dichlorbenzene and the resulting solution was washed successively with dilute hydrochloric acid and water. The washed product was then fractionally distilled under vacuum whereby there was obtained 236 grams (88 per cent of the theoretical yield) of tri-p-tertiarybutyl-o-tolyl phosphate, a. colorless viscous liquid distilling at approximately 304 to 308 C. under 8 millimeters pressure and having an index of refraction,

Tri-p-tertiarybutyl-o-tolyl phosphate has the formula:

Example 2 A mixture or 150 grams (1.0 mol) of ptertiaryoxychloride, and 1.0 gram of magnesium metal was heated at a temperature of 80 to 88 C. for 1 hour during which time 0.95 mol of hydrogen chloride was evolved from the mixture. The excess phosphorus oxychloride was then distilled from the mixture, 1.91 mols being recovered.

' The crude p-tertiarybutylphenyl phosphoric acid dichloride was then cooled and 328 grams (2.0 mols) of p-tertiarybutyl-o-cresol was added. The mixture was heated at 160 C. for 6% hours after which time it was blown with air for 1 hour to remove last traces of hydrogen chloride. The crude phosphate product was then diluted with o-dichlorbenzene, washed, and iractionally distilled as in Example 1. There was obtained 433 grams (82.8 per cent of the theoretical yield) of di-p-tertiary butyl-o-tolyl mono-p-tertiarybutyl phenyl phosphate, a viscous colorless liquid distilling at approximately 310 to 314 C. under 8 millimeters pressure and having a specific gravity of about 1.070 at 25/25 C. and an index of refraction,

This compound has the formula:

Example 3 A mixture of 246 grams (1.5 mols) of p-tertiarybutyl-ocresol, 694 grams (4.5 mols) of phosphorus oxychloride, and 1.5 grams of magnesium metal was heated at 80 to 90 C. for 1 hour, after which time the excess phosphorus oxychloride was distilled from the mixture. 510 grams (3.0 mols) of p-phenylphenol was then added and the mixture was heated at C. for 8 hours. and washed to remove hydrogen chloride, as in Example 2, and was fractionally distilled under vacuum. There wascbtained 632.5 grams (77 per cent of the theoretical yield) of p-tertiarybutyl-o-tolyl di-p-xenyl phosphate, :9. pale-yellow viscous liquid distilling at approldmatelyil'lfi to 385 C. under 8 millimeters pressure and having an index of refraction,

and the formula:

Other triaryl phosphates of the present class The mixture was then blown with air 76 butylphenol, ass grams (3.0 mole) of phosphorus which have been prepared by procedure similar ll to that set forth in the above examples are set forth in the :tollowing table:

' Table Compound Distillation Specific I d 1 MW seat:-

Name Formula O.

OH: on oOo-cm p-Terti bntyl-o-tol idion o 1 x vis- I p-terti zrybutyl-phznyl CHg-JIOO-P i a Zoii fiuid. Bum, L068 I'm phosphate. (I) OH:

ta. cim

a 0 Tettisrybutyl'o-tolyldlcm M am 345 1.162 1.5854 o-zany] phosphate. OKs-i 0- 00H; 0 V

' cm 03 cm 0 c 0m Di-p-tertisrybu l-o-to yl Ha mono-phenylp osphato OKs- OE\ 1 do esocozsa 1.698 1.5272

The phenolic reactants otherthan p-tertiary- 2. A liquid triaryl phosphate the genbutyl-o-cresol employed in preparing mixed trieral formula: I aryl phosphates of the present class may contain H any of the neutral substituents, such as halogen, cm 0 aryl, alkyl, or cycloalkyl substituents,- which are OH 6 non-reactive with phosphorus oxyhalicle under "'6 O- the reaction conditions employed, in which case R, n correspondingly substituted triaryl phosphates will be obtained. Certain of such substituted triaryl phosphates have been described in the foregoing examples and table. Other phosphates of this type are: p-tertiarybutyl-o-tolyl di-naphthyl phosphate, di-p-tertiarybutyl-o-tolyl mono-2,4-

dichlorphenyl phosphate, p-tertiarybutyl-o-tolyl.

di-2-methyl-S-isopropylphenyl phosphate, p-tertiarybutyl-o-tolyl di-p-cyclohexylphenyl phosphate, di-p-tertiarybutyl-o-tolyl mono-p-tertiaryoctylphenyl phosphate, p-tertiarybutyl-o-tolyl -di-2,4,6triethylphenyl phosphate, etc.

Other modes of applying the principle of my invention may be employed instead oi those explained, change being made with regard to the method or terms employed provided the products stated by any of the following claims be obtained.

I therefore particularly point out and distinctly claim as my invention:

1. A liquid triaryl phosphate having the general formula:

wherein R represents an aryl radical and n and n each represents an integer, the sum of 1: and n being equal to 3.

wherein n and 1: each represents an integer, the sum of n and n being equal to 3, and n" represents an integer not greater than 3.

4. A liquid triaryl phosphate having the general formula:

OH CH:

G V AH: a

wherein n and n each represents an integer, the sum of n and n being equal to 3.

5. 'Iri-p-tertiarybutyl-o-tolyl phosphate, a colorless viscous liquid distilling at approximately 5 304 to 308 0. under 8 millimeters pressure, and

having an index of refraction,

8. Di-p-tertiarybutylphenyl mono p-tertiarybutyl-o-tolyl phosphate, a. colorless viscous liquid distilling at approximately 314 to 318 C. under 8 millimeters pressure, and having a specific {gravity 0! about 1.068 at 25/25 0. and the for-- mula:

7. Di-p-xenyl mono-p-tertiarybutyl o tolyl phosphate, 9. pale-yellow viscous liquid distilling at approximately 378 to 385 C. under 8 millimeters pressure, and having an index of reirac- 15 11B 1.5954 and the formula:

CLARENCE L. MOYLE.

Cari a s\ "Gig ,0 

